Compositions containing quaternary ammonium salts



United States Patent 3,329,609 COMPOSITIONS CONTAINING QUATERNARY AMMONIUM SALTS Rodney A. Blomfield, Grosse lle, Mich., assignor to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan No Drawing. Filed Mar. 22, 1965, Ser. No. 441,871 Claims. (Cl. 252,8.8)

ABSTRACT OF THE DISCLOSURE Cation-active quaternary ammonium salts are compatible with certain polyvalent anion-active salts of hydrofluorosilicic acid. These salts may be used in aqueous solutions to impart softness and bacteriostatic activity to hair and cellulosic materials such as textiles and paper. Auxiliary additives, such as optical brighteners, inert fillers, dyes, perfumes, etc., may be added to the mixture of quaternary ammonium salts and salts of hydrofiuorosilicic acid.

This invention relates generally to surface active agents and more particularly to quaternary ammonium salt compositions for imparting softness and bacteriostatic activity to hair and cellulosic materials, such as textiles and paper.

The quaternary ammonium salts, being cationic" or cation-active agents, are not considered compatible with anion-active materials. It is generally believed that quaternary ammonium salts are precipitated or rendered inactive by organic anion-active materials such as soaps, alkyl aryl sulfonates, other anionic synthetic detergents, and carboxymethyl cellulose. Also, the polyvalent inor ganic anions, such as the phosphates and sulfates, act as precipitants of the quaternary ammonium salts.

Commercial forms of quaternary ammonium salts useful for imparting softness and ibacteriostatic activity to textiles are usually viscous pastes or liquids containing water and organic solvents. Recently commercial forms of the quaternary ammonium salts have been prepared as 100% active powders. The powdered forms are preferred because of their ease of handling and lower packaging costs. However, preparing useful powdered compositions with these products is diflicult since the phosphates and sulfates used in the formulation of these powdered products act as precipitants of the quaternary ammonium salts under use conditions.

The incompatibility between quaternary ammonium salts and the above-mentioned materials can be a serious problem. The effective utilization of the quaternary ammonium salts for their functional benefits may be diminished as a result of this incompatibility. The incompatibility results in non-uniform and ineffectual softening and localized areas which are poorly absorbent, all undesirable properties.

As pointed out in U.S. Patent No. 3,154,489, any anion-active organic or polyvalent inorganic anionic materials added to the quaternary ammonium salts generally are found not to aid the quaternary ammonium salts in their function as softening agents. These added materials generally constitute in effect waste materials.

Hagge et al., U.S. Patent No. 2,734,830 disclose a process for washing and softening textile goods that are usually repeatedly laundered. I have found, however, that the softening agents disclosed by Hagge et al. when used either in the rinse cycle of an ordinary laundry operation or in a separate bath following the rinse cycle are not uniformly distributed upon the surface of the fabrics treated if sulfate, phosphate or organic anions are present.

An excellent review of the chemical and physical "ice properties of some of the more commercially important cationics is presented by Speel and Schwarz, Textile Chemicals and Auxiliaries, second edition, Reinhold Publishing Corporation, 1957. In chapter 18, Speel and Schwarz, at page 395, state that many cationic finishing agents interfere with the production of suitable whites. It is also known that there is a tendency for laundered articles to yellow When treated with cationic agents. This yellowing of the textiles treated with cationics is believed to be caused by 1) highly colored impurities or byproducts in some commercial cationic finishing agents or (2) the presence of high amounts of iron in the finishing agents that may cause staining typical of iron compounds or, (3) due to the presence of alkali when the materials treated with the cationics are ironed or pressed.

It is known that one class of the cationics, the quaternary ammonium salts, exhibits germicidal or bacteriostatic properties and exert a controlling effect upon mildew and other fungi. As pointed out above, the quaternary ammonium salts are precipitated or rendered inactive by certain anion-active organic or poly-valent inorganic anionic materials. The germicidal properties of the quarternary ammonium salts are also diminished by the presence of organic anion-active and inorganic polyvalent anionic materials.

It is therefore an object of this invention to provide compositions useful for imparting softness to fabrics.

It is another object of this invention to provide compositions for imparting bacteriostatic properties to materials treated with the compositions.

Another object of this invention is to provide a fabric softening composition which imparts a combination of uniform softness and bacteriostat'ic properties to the fabrics treated therewith. I

A further object of this invention is to provide a cationic-containing composition which shOWs no tendency to yellow fabrics treated therewith.

A still further object of this invention is-to provide a fabric softening composition including quaternary ammonium salts and polyvalent inorganic anionic material.

These and other objects will become apparent as this specification proceeds.

The present invention lies in the discovery of polyvalent anion-active materials that are compatible with the cationic active quaternary ammonium salts. It is generally believed as disclosed in U.S. Patent No. 3,154,- 489, that the quaternary ammonium salts are precipitated or rendered inactive by all organic anion-active materials and polyvalent inorganic anion-active materials. It was surprising, in view of this, to discover a series of polyvalent inorganic anionic compounds) compatible with quaternary ammonium salts. It was even more surprising to learn that the polyvalent inorganic anionic materials of this invention actually enhance the desirable properties of the quaternary ammonium salt fabric softener compositions and quaternary ammonium salt bacteriostatic compositions. The polyvalent inorganic anionic materials of this invention, when formulated with quaternary ammonium salts, form acid solutions which help prevent the yellowing of textiles. The yellowing of textiles is believed to be due to the presence of alkali when the textiles are ironed or pressed.

The compositions of the instant invention comprise quaternary ammonium salts and salts of hydrofluorosilicic acid. Filler materials that will not precipitate quaternary ammonium salts are also usually included in the compositions. The filler materials are not necessary but are merely used as a means to facilitate the measuring of the compositions by the ultimate consumer. Therefore, any compatible filler material may be used with the compositions of this invention.

The compositions of this invention are very readily 3 wherein R is a fatty acid radical containing from 10 to 22 carbon atoms; R is selected from the group consisting of (1) an alkyl radical containing less than 3 carbon atoms, (2) a benzyl radical, (3) an alkylphenoxyethoxyethyl radical having the formula (4) an alkylcresoxyethoxyethyl radical having the formula wherein A is an alkyl radical having 8 to 18 carbon atoms, and an alkyl benzyl radical having the formula wherein A is as indicated above; R is an alkyl radical containing less than 3 carbon atoms; and X represents an anion selected from the group consisting of chloride, bromide, sulfate and alkyl sulfate in which the alkyl radical contains less than 5 carbon atoms.

The R fatty acid radical in the above formulae may be a natural mixture thereof derived from tallow, soybean or coconut oil. The R fatty acid radical may also be olefinic, diolefinic, acetylinic or otherwise unsaturated. Specific examples of fatty acid radicals that can be used in the compositions of this invention include decanoic, decenoic, undecanoic, undecenoic, dodecanoic, dodecenoic, tridecanoic, tridecenoic, teitadecanoic, tetradecenoic, pentadecanoic, pentadecenoic, hexadecanoic, hexadecenoic, heptadecanoic, heptadecanoic, octadecanoic, octadecenoic, nonadecanoic, nonadecenoic, eicosanoic, eicosenoic, docosanoic and docosenoic radicals.

It is known that the cationic surface active agents, which include a greater number of short-chain alkyl groups in the structure, incline toward better bacterio static properties. Therefore, Formula 1 above would generally represent the bacteriostatic agents. Specific examples of bacteriostatic agents that may be used in the compositions of this invention include di-isobutyl cresoxy ethoxy ethyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl trimethyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl allyl ammonium chloride, methyl dodecylbenzyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, octadecyl dimethyl ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, octadecenyl-Q-dimethyl ethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecynyl trimethyl ammonium bromide, hexadecynyl trimethyl ammonium iodide, octyl trimethyl ammonium fluoride, and mixtures thereof. Other water dispersible salts, such as the acetates, sulfates, nitrates, and phosphates, are effective in place of the halides, but the chlorides are preferred.

The cationic surface active agent with a larger number of long-chain alkyl groups demonstrate superior fabric softening properties. The preferred quaternary ammonium salt softening agents have at least two long-chain alkyl groups attached to the nitrogen atom. The compounds are represented in general by Formula 2 above. It is preferred that the long-chain alkyl groups contain between 10 and 22 carbon atoms. Particularly effective quaternary ammonium salt fabric softeners are the dialkyl dimethyl ammonium chlorides Where the alkyl chains are composed of aliphatic chains ranging from 10 to 22 carbon atoms. Of particular importance to this invention are dimethyl distearyl quaternary ammonium and dimethyl dihydrogenated tallow quaternary ammonium chlorides. The tallow quaternary ammonium chloride is a mixture of fatty acid derivatives consisting of about 2. 0% myritisc, 32.5% palmitic, 14.5% stearic, 48.3% oleic and 2.7% linoleic. Quaternary ammonium derivatives of the soybean and coconut fatty acids can also be used as the softening agents within the scope of this invention.

The polyvalent inorganic anionic materials that are compatible with the cationic quaternary ammonium salts are the salts of hydrofluorosilicic acid. Examples of hydrofluorosilicic acid salts that can be used in the compositions of this invention include ammonium fluosilicate, calcium fluosilicate, strontium fluosilicate, barium fluosilicate, lead fiuosilicate, magnesium fluosilicate, potassium fluosilicate, sodium fluosilicate, lithium fluosilicate, and zinc fluosilicate. These compounds are also called silicofluorides. In preferred embodiments of this invention, the compositions contain the ammonium, sodium and zinc hydrofluorosilicic acid salts and mixtures thereof.

The inert filler materials for use with the compositions of this invention may be described as any inorganic compound that exhibits monovalent anions and when in an aqueous solution. Suitable compounds include the alkali and alkaline-earth metal amides, bifluorides, halides, metaborates, metaphosphates, nitrates, nitrites and perborates. The preferred alkali metals are sodium, potassium and lithium. The preferred alkaline-earth metals are calcium and magnesium.

The treating compositions for softening fabrics in accordance with this invention comprise from about 20 to of a quaternary ammonium salt in accordance with Formula 2 above as the softening agent, from about 20 to 80% of a salt of hydrofluorosilicic acid and from zero to 25% of an inert filler material.

The treating compositions for imparting bacteriostatic properties to fabrics comprise from about 8% to 80% of a quaternary ammonium salt bacteriostatic agent in accordance with Formula 1 above, from about 20 to 80% of a salt of hydrofluorosilicic acid and from zero to 25% of an inert filler material.

Treating compositions having properties for both softening and imparting bacteriostatic properties to fabrics as disclosed by this invention comprise from about 20 to 80% of a quaternary ammonium salt softening agent, from about 5 to 15% of a quaternary ammonium salt bacteriostatic agent, from about 20 to 80% of a salt of hydrofluorosilicic acid and from zero to 25 of an inert filler material. Thus, the compositions of this invention, in general, contain mixtures of a quaternary ammonium salt and a salt of hydrofluorosilicic acid wherein the weight ratio of these two components may range from 4:1 to

The compositions of this invention may be prepared by simply blending all the dry ingredients in a mixer such as a ribbon mixer. Any or all of the auxiliary additives such as perfumes, optical brighteners, dyes, etc. may also be blended into the compositions at the same time.

A more comprehensive understanding'of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of the invention.

6 Examples 21-22 To illustrate the effectiveness of the compositions in controlling the yellowing of fabrics, the compositions of Examples 21 and 22 of Table II were prepared.

Fourteen grams of cotton Indlan Head muslin was cut Exam les 1-20 p into twenty 2 /2" by 3 /2" swatches. The twenty test The compositions shown in Table I hereinafter, were stvlvatches were placed m Terg'O'TOmeteI cpn'tammg prepared and treated as described below The composit teilths gram of composltlqn t to one hter of detions of Examples 1 2 3 8 9 12 14 and 19 are 10 mineralized water at 80 F. Agltatlon of the test swatches 2 2 a a a 5 a a a in accordance with the present invention While the continued for 10 minutes at 60 c.p.m. Excess solution was positions of the other examples have been included as removed from the test swatches in a hydroextractor and controls. Three tenths gram of composition was added to the swatches were pressed dry on a Steam press The one liter of demineralized water at 80 F. contained in reflectance the Swatches was measufgd before and after a Terg-O-Tometer. Fourteen grams of cotton Indian treatment wl'th of composltlons on a Hunter Head muslin cut into twenty 21/2 I, by 31/2 Swatches was Refiectometer uslng amber, blue and green filters. The readded to the Solution and agitation Started at 60 C p m flectances were calculated as yellowness 1nd1ces and the ex- After 10 minutes the swatches were removed from the tent of yellowmg calculated' Yellowness index calm solution. Excess solution was removed from the swatches gi g g ig fi gi reflectapce fi g i g in a hydroexitractor and the swatches were pressed dry on e i ance usmg- 6 am er an a Steam mass. The Swatches were then immersed in a then the remainder is d1v1ded by reflectance us ng the green 0 01% Solution of bromophenol b1 ue which forms a blue filter. Table II shows that swatches treated with composicmplex with quaternary ammonium Salts After rinsing tions of this invention have a decrease in yellowness as in deminerafized Water the Swatches were examined for compared to the untreated swatches. Swatches treated with intensity and uniformity of deposition of the quaternary quaternary i q sallt comp0s1.nonS havmg inqi'gamc ammonium Salt compound onto the fabric The more polyvalent amonic materials therein show a sigmficant intense and uniform the deposition the greater the soften- Increase In the tendency to yellow ing and/ or bacteriostatic activity imparted to the fabric. TABLE H Examples 4, 5, 6, 7, 11, 15, 16, 17, 18, and 20 show that the polyvalent sulfate and phosphate anions precipitate Example the quaternary ammonium salt in the use solutions and Ingredients cause non-uniform deposition onto the fabric with re- 21 22 sultant poor softening and/or bacteriostatic activity. The quaternary ammonium salts are not precipitated by the Dimethyr Dihydrogenated Tallow Quaternary polyvalent silicofluoride anions as shown in Examples 1, ft g b g gg gg-g 1 12, 14, and permitting h vy and Nisirfi .93...?..- 1:::::::::::::: "II "are; uniform depositions onto the fabric. Thus, it can be seen ggfiggggg: E33 gag%ggagggg 8 35 ggggi that uniform softening and/or bacteriostatic properties Percentlncreasein Yellowness g '4o.5 are imparted to the fabrics by the compositions of this PercentDecTeasem Yellwness 201 invention.

TABLE I Example Ingredient Intensitypf deposition of cationic Heavyon fabric.

Heavy Uniformity of deposition of Uniform. Uniform- Uniform Non-unl- Non-uni- Non-uni- Uniform. Uniform cationic on fabric. form form. form.

Example Ingredient Light Light.

on fabric. Uniformity of deposition of Non-uni- Uniform- Uniform Uniform. Non-uni- .Non-uni- Nornuni- Non-uni- Uniform. Non-unicationic on fabric. form. form form. form. form form.

A -Dimethyl dihydrogcnated tallow quaternary ammonium chloride (190% active powder, fabric softening agent). B Diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chlorlde active powder, a bacteriostatic agent).

7 Examples 23-25 Table III ilustrates the use of diisobutyl phenoxyethoxyethyl dimethyl ammonium chloride in composition to treat textiles and papers to impart only bacteriostatic properties thereto. The test swatches were treated in the same manner as the test swatches of Table I.

Example 23 shows that the polyvalent sulfate ion in the composition results in light deposition on the fabric. Example 24 shows that the monovalent inorganic anions do not have this undesirable effect. Example 25 shows that the use of a salt of hydrofluorosilicic acid provides a heavy and uniform deposition on the treated swatches. The uniformity of deposition on the fabric by the bacteriostatic composition containing Na SO is believed to be due to the fine precipitate formed by the quaternary ammonium salt and the sulfate ion. A fine precipitate would have a tendency to distribute itself evenly over the test swatch.

Twenty Indian Head muslin swatches 2 /2" 'by 3 /2 treated with a composition having the formulation of Example 10, were evaluated for bacteriostatic effectiveness. The swatches were treated in accordance with the procedure set out above. After the swatches were pressed dry on a steam press, the swatches were inoculated with Staphylococcus aureus ATCC6538 bacteria in accordance with Test Method 100-1961T. A desrciption of this test method may be found in the 1962 Technical Manual of the American Association of Textile Chemists and Colorists, vol. 38, pages B131-132. The test method is entitled Evaluation of Antibacterial Finishes on Fabrics." The evaluation of the test swatches showed that none of the bacteria survived when the swatches were treated with compositions of this invention in accordance with this test method and at the concentration of the formulation of Example 10.

Numerous variations nad modifications of the invention will occur to those skilled in the art upon reaching this disclosure. It is to be understood that all such variations and modifications are intended to come within the spirit and scope of the invention as defined in the appended claims.

I claim:

1. A composition for treating textiles in an aqueous solution to impart softness thereto comprising from 20 to 80 Weight percent of a quaternary ammonium salt having the general formula:

wherein R is a fatty acid radical containing from 10 to 22 carbon atoms; R is an alkyl radical containing less than 3 carbon atoms; and X represents an anion selected from the group consisting of chloride, bromide, sulfate, and alkyl sulfate in which the alkyl radical contains less than 5 carbon atoms and from about 80 to 20 Weight percent of a salt of hydrofluorosilicic acid selected from the group consisting of ammonium fluosilicate, calcium fluosilicate,

wherein R is a fatty acid radical containing from 10 to 22 carbon atoms; R is selected from the group consisting of (1) an alkyl radical containing less than 3 carbon atoms, (2) a benzyl radical, (3) an alkylphenoxyethoxyethyl radical having the formula (4) an alkylcresoxyethoxyethyl radical having the formula wherein A is an alkyl radical having 8 to 18 carbon atoms, and (5) an alkyl benzyl radical having the formula where A is as indicated above; R is an alkyl radical containing less than 3 carbon atoms; and X represents an anion selected from the group consisting of chloride, bromide, sulfate, and alkyl sulfate in which the alkyl radical contains less than 5 carbon atoms and from about to 20 Weight percent of a salt of hydrofluorosilicic acid selected from the group consisting of ammonium fluosilicate, calcium fluosilicate, strontium fluosilicate, barium fluosilicate, lead fiuosilicate, magnesium fiuosilicate, potassium fluosilicate, sodium fluosilicate, lithium fluosilicate, zinc fiuosilicate, and mixtures thereof.

3. A composition for imparting softness and bacteriostatic properties to textiles in an aqueous solution comprising from about 20 to 80 weight percent of a quaternary ammonium salt softening agent having the general formula:

and from about 5 to 10 weight percent of a quaternary ammonium salt bacteriostatic agent having the general formula:

wherein R is a fatty acid radical containing from 10 to 22 carbon atoms; R is selected from the group consisting of (1) an alkyl radical containing less than 3 carbon atoms, (2) a benzyl radical, (3) an alkylphenoxyethoxyethyl radical having the formula (4) an alkylcresoxyethoxyethyl radical having the formula wherein A is an alkyl radical having 8 to 18 carbon atoms, and an alkyl benzyl radical having the formula wherein A is as indicated above; R is an alkyl radical containing less than 3 carbon atoms; and X represents an anion selected from the group consisting of chloride, bromide, sulfate, and alkyl sulfate, in which the alkyl radical contains less than 5 carbon atoms and from about 80 to 20 Weight percent of a salt of hydrofluorosilicic acid selected from the group consisting of ammonium fluosilicate, calcium fluosilicate, strontium fluosilicate, barium fluosilicate, lead fluosilicate, magnesium fluosilicate, potassium fluosilicate, sodium fluosilicate, lithium fluosilicate, zinc fluosilicate, and mixtures thereof.

4. A composition for treating textiles in an aqueous solution to impart softness thereto comprising from about 20 to 80 Weight percent dimethyl dihydrogenated tallow quaternary ammonium chloride and from about 80' to 20 weight percent of a salt of hydrofluorosilicic acid selected from the group consisting of ammonium fluosilicate, sodium fluosilicate, zinc fluosilicate and mixtures thereof.

5. The composition of claim 4 including from about to 25 weight percent of a filler material selected from the group consisting of sodium chloride and sodium nitrate.

6. A composition for treating textiles in an aqueous solution to impart bacteriostatic properties thereto comprising from about to 80 weight percent diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride and from about to 20 weight percent of a salt of hydrofluorosilicic acid selected from the group consisting of ammonium fluosilicate, sodium fluosilicate, zinc fluosilicate and mixtures thereof.

7. The composition of claim 6 including from about 15 to 25 weight percent of a filler material selected from the group consisting of sodium chloride and sodium nitrate.

8. The composition of claim 1 including from about 15 to 25 weight percent of a filler material selected from the group consisting of the alkali and alkaline-earth metal amides, bifluorides, halides, metaborates, metaphosphates, nitrates, nitrites, perborates and mixtures thereof.

9. The composition of claim 2 including from about 15 to 25 Weight percent of a filler material selected from the group consisting of the alkali and alkaline-earth metal amides, bifluorides, halides, metaborates, metaphosphates, nitrates, nitrites, perborates and mixtures thereof.

10. The composition of claim 3 including from about 15 to 25 weight percent of a filler material selected from the group consisting of the alkali and alkaline-earth metal amides, bifiuorides, halides, metaborates, metaphosphates, nitrates, nitrites, perborates and mixtures thereof.

References Cited UNITED STATES PATENTS 2/1956 Haage et a1 2528.8 7/1962 Brunt et al. 2528.75 

1. A COMPOSITION FOR TREATING TEXTILES IN AN AQUEOUS SOLUTION TO IMPART SOFTNESS THERETO COMPRISING FROM 20 TO 80 WEIGHT PERCENT OF A QUATERNARY AMMONIUM SALT HAVING THE GENERAL FORMULA: 